Bioresource Technology 101 (2010) 2458–2465

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Average structural analysis of tar obtained from pyrolysis of wood

Diana López *, Nancy Acelas, Fanor Mondragón
Institute of Chemistry, University of Antioquia, A.A. 1226, Medellín, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: Conventional analytical methods such as 1H NMR, vapor pressure osmometry (VPO) and elemental anal-
Received 17 September 2009 ysis were used to characterize the tar obtained from pyrolysis of pine.
Received in revised form 5 November 2009 The major fraction of tar obtained during pyrolysis of pine at different temperatures was the insoluble
Accepted 7 November 2009
fraction in n-heptane which corresponds to asphaltenes; this fraction was characterized and analyzed
Available online 4 December 2009
using average structural parameters. The structural unit of the tar is composed of one aromatic ring substi-
tuted by aliphatic chains, olefinic groups and the presence of oxygenated groups. Two of such average
Keywords:
structures determined with this methodology corresponds to 4-formyl-2,6-dimethoxy-3-[(1E)-prop-1-
Tar
Pyrolysis
en-1-yl]-5-propylbenzoic acid and 2,3,5-trimethoxy-6-[(1E)-prop-1-en-1-yl]-4-propylbenzaldehyde.
Nuclear magnetic resonance Ó 2009 Elsevier Ltd. All rights reserved.
Average structural parameters

1. Introduction as a function of process temperature from primary products to

Amongst the renewable energies, one of the most important en-
ergy sources in near future is biomass. The thermochemical trans-
formation of biomass generates gases, liquids and solid fuels; these
derived products can partially replace fossil fuels in order to pro-
duce heat, electricity and/or chemical products (Encinar et al.,
2000). Among all the procedures used to transform biomass into
useful products, pyrolysis and gasification are the most appropri-
ate methods. However, large amount of condensable organic
compounds is evolved in biomass gasification and the presence
of tar causes blockages and corrosion of pipes and also reduces
the overall thermal efficiency of the system (Fassinou et al., 2009).
Tar is defined as a complex mixture of condensable hydrocar-
bons, which may be composed of 1–5 aromatic ring compounds
along with other oxygen-containing hydrocarbons and complex
polycyclic aromatic hydrocarbons (PHA); its composition strongly
depends on the reaction conditions as a consequence of the com-
plex reactions that take occur during the pyrolysis and gasification
processes (Milne et al., 1998; Yanik et al., 2007; Chunshan and
Kenzi, 2008). Therefore, appropriate characterization of the
mixture of compounds is required in order to find a possible
application and hence a possibility of control in their production.
Most of the research on tar characterization has been on pyro-
lysis products obtained at high temperatures, for example, Elliott
(Elliot, 1981; Chunshan and Kenzi, 2008) proposed the sequence
presented in Scheme 1 for the composition of biomass pyrolysis
products from various processes. Scheme 1 shows the transition
* Corresponding author. Tel.: +57 4 2196613; fax: +57 4 2196565.
E-mail address: diana_lopez@yahoo.com (D. López).
phenolic compounds to aromatic hydrocarbons.
Several analytical techniques have been used to describe the
structural composition of petroleum fractions. In particular, proton
and carbon nuclear magnetic resonance techniques have been use-
ful to determine the structural skeleton of several fossil fuels (Wil-
liams, 1958; Brown and Ladner, 1960; Clutter et al., 1972; Cantor,
1978; Satou et al., 1991; Guillen et al., 1998; Lee and Glavincevski,
1999; Yang et al., 2003; Yan et al., 2005; Patrakov et al., 2005). Nev-
ertheless, neither the NMR spectra, nor other spectroscopic and
analytical data provide enough information to completely delin-
eate the individual components of a mixture. Therefore, due to this
complexity, and the need to represent the composition of these
fractions in a systematic way, the concept of ‘‘average structure”
has arisen. The determination of these structures is generally based
on nuclear magnetic resonance information combined with ele-
mental analysis and molecular weight (Clutter et al., 1972; Satou
et al., 1991; Lee and Glavincevski, 1999). The intent of this ap-
proach is to characterize the soluble and insoluble fractions in a
particular solvent using average structural parameters that later
can be used to outline the possible average chemical structures.
Although this type of analysis has been routinely used to charac-
terize liquid oil and coal liquid fractions (Williams, 1958; Brown
and Ladner, 1960; Clutter et al., 1972; Cantor, 1978; Satou et al.,
1991; Guillen et al., 1998; Lee and Glavincevski, 1999; Yang
et al., 2003; Yan et al., 2005; Patrakov et al., 2005), to the
knowledge of the authors it has not been used to characterize tar
fractions from biomass.
Therefore, the purpose of this study is to obtain chemical struc-
ture information of the n-heptane insoluble fraction of tar gathered
from pyrolysis of pine through average structural parameters such

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.11.036
 D. López et al. / Bioresource Technology 101 (2010) 2458–2465
Scheme 1. Sequence of transformations induced by temperature proposed by Elliott.
as aliphatic chain length, number of fused aromatic rings, and
number of substituents per aromatic cluster, using conventional
analytical techniques such as 1H NMR, vapor pressure osmometry
(VPO) and elemental analysis.
2. Methods
2.1. Material
The sample employed in this study was cypress pine. Prior to the
pyrolysis experiments, the sample was milled to an average size of
0.25 mm, and it was then dried for 2 h at 100 °C. The results of
their proximate analysis indicate an 82 wt.% of volatile matter,
17.1 wt.% of fixed carbon and 0.91 wt.% of ash in a dry basis and
the ultimate analysis gives 39.9% C, 5.34% H and 54.7% O.
2.2. Pyrolysis and tar fractioning
Pyrolysis experiments were carried out at temperatures be-
tween 250 °C and 400 °C in a tubular fixed-bed reactor at atmo-
spheric pressure under nitrogen flow. Fig. 1 illustrates the
apparatus, which is mainly made of a quartz tubular reactor, a
heated off-gas line, and a salt-ice cooling trap. The tube had a
length of 614 mm and an inside diameter of 22 mm, and it was
externally heated by an electric furnace. The wood sample was
held on a plug of quartz wool, which was placed on a supporting
mesh at the center of the reactor. Nitrogen was fed into the system
at a flow rate of 100 ml/min for about 2 h. The temperature was
Fig. 1. Schematic diagram of experimental apparatus. (1) Nitrogen supply, (2) thermocouple, (3) quartz tube, (4) furnace, (5) tar collector and salt-ice cooling trap, (6) vent,
and (7) temperature controller.
2459
monitored with a thermocouple attached to the reactor external
wall, closed to the sample. The samples were heated at 20 °C/min
to the reaction temperature, 200, 300, 350 and 400 °C.
The oily products condensed in the salt-ice cooling trap were
mixed with n-heptane following a common procedure in the petro-
leum industry to separate crude oil in different fractions (Demir-
bas, 2002). The fraction soluble in n-heptane is called maltenes
and the insoluble faction is called asphaltenes, this latter is a com-
plex hydrocarbon mixture composed of aromatic compounds with
alkyl side chains and heteroatomic side-chain functional groups.
The main fraction obtained in this study was the insoluble part
in n-heptane, which was characterized and analyzed by the aver-
age structural parameters.
2.3. 1H NMR analysis
1
H NMR spectra were carried out on the fraction insoluble in n-
heptane (asphaltenes) obtained at different temperatures, the frac-
tions were re-dissolved in CDCl3 containing a trace amounts of tet-
ramethylsilane (TMS), which was used as internal chemical shift
reference. All spectra were taken in a Bruker AMX 300 spectrome-
ter, using a 5 mm inner diameter sample holder.
Before starting the analysis, the obtained spectra were treated
for phase and baseline corrections using the NMR notebook pro-
gram. Each spectrum was separated into eight typical regions that
correspond to eight different protons (Hald, Ha, Ho, Hf, Hmet, Ha, Hb y
Hc), according to their position in the molecule (see Table 1). The
integration of the spectra was carried out manually, a minimum
2460 D. López et al. / Bioresource Technology 101 (2010) 2458–2465

Table 1 Table 2
Chemical shifts for the different type of protons (Williams, 1958; Cantor, 1978; Average structural parameter definitions.
Guillen et al., 1998).
C* Molar fraction of carbon obtained by elemental analysis
Symbol Type of proton Chemical H* Molar fraction of hydrogen obtained by elemental analysis
shifts (ppm) O* Molar fraction of oxygen obtained by elemental analysis
MW Average molecular weight
Hald Aldehyde proton adjacent to an aromatic ring 9.0–10.0
fa Fraction of aromatic carbon
Ha Aromatic hydrogen 6.3–8.4
fal Fraction of aliphatic carbon
Ho Olefinic hydrogen 4.5–6.3
fa(f) Fraction of a and (f) fluorene-type carbon attached to aromatic rings
Hf Fluorene-type hydrogen 4.0–4.5
faHa Fraction of aromatic carbon substituted by aromatic hydrogen
Hmet Hydrogen in O–CH3 and O–CH2 groups 3.5–4.0
fo Fraction of carbon in olefinic groups
Ha Hydrogen on a carbons to aromatic rings 2.0–3.5
fald Fraction of carbon in carbonyl groups of aldehyde
Hb Hydrogen on b carbons to aromatic rings 1.0–2.0
fmet Fraction of carbon in O–CH3 and O–CH2 groups
Hc Hydrogen on c carbons or CH3 terminal of aliphatic 0–1.0
%Ci Weight fraction of Ci carbon, with i = a, al, a. . .
chains alkylating an aromatic ring
#Ci Average number of Ci carbons per average structural unit, with i = a,
al, a. . .
ðC=HÞal C/H molar ratio in aliphatic groups
L Chain length number per average structural unit
of six times, and the results were averaged to reduce the uncer-
tainty (less than 5%) generated by the manual adjustment.

The equations used to calculate the average structural parame-

2.4. VPO measurements
ters are summarized in Table 3. The variables Hald , Ha , Ho , Hf , Hmet ,
Ha , Hb and Hc , correspond to the molar fraction of the normalized
Average molecular weight data of the insoluble tar fraction in n-
integrals of the different types of hydrogen identified in the 1H
heptane (asphaltenes) was determined by vapor pressure osmom-
NMR spectra; whereas, the variables C*, H* and O* correspond to
etry (VPO) in a Knauer osmometer using tetrahydrofurane (THF) as
the molar fraction of carbon, hydrogen and oxygen coming directly
solvent and benzyl as calibration standard. All measurements were
from elemental analysis.
carried out using sample and standard solutions of 11 g/kg and
In the derivation of the equations used in this study, several
0.054 mol/kg, respectively. Then, the average molecular weight
assumptions must be taken into account to determine these
(MW) was obtained from the kcal/Ks ratio, where kcal is the benzyl
parameters. First, the alkyl and oxygenated groups present in the
calibration constant expressed in kg/mol and Ks is the sample con-
sample are attached directly to aromatic rings. Second, the ali-
stant, which is expressed in kg/g. The minimum molecular weight
that can be determined by this technique using organic solvents is
about 40 g/mol.
Table 3
Average structural parameter equations.
2.5. Elemental analysis
2          3
C  0:33Hc þ 0:4 Hb þ Hmet þ 0:5 Ha þ Hf þ Hald þ Ho
fa ¼ 4 5 ð1Þ
The elemental analysis of the samples was carried out by the C
conventional combustion method using a Perkin–Elmer CHN ana-
2       3
lyzer. Oxygen content was obtained by difference. 0:33Hc þ 0:4 Hb þ Hmet þ 0:5 Ha þ Hf
fal ¼ 4 5 ð2Þ
C
2.6. Average structural parameters calculations "   #
0:5 Haðf Þ
1
faðf Þ ¼  ð3Þ
Some of the first studies that used H NMR analysis to obtain C
average structural parameters in complex mixture of hydrocarbons "   #
0:4 HaðmetÞ
were published by Williams (1958) and Brown and Ladner (1960). fbðmetÞ ¼  ð4Þ
C
In these studies the authors reported a set of structural parameters
such as aromaticity (fa), substitution degree (r), branching index "   #
0:3 Hc
(BI), and aromatic condensation index, which were used to de- fc ¼ ð5Þ
C
scribe some heavy oil fractions. Years later, Clutter et al. (1972) ex-
 
tended the model implemented by the former authors by ðHa Þ
fðaHaÞ ¼  ð6Þ
introducing 13C NMR analysis in the interpretation of their results. C
Although nowadays there are much more precise models to de- 
ðHo Þ 

scribe complex mixtures of hydrocarbons, they are also much more f0 ¼ ð7Þ
C
complex and difficult to apply. Also, it is necessary to have a broad  
knowledge of the chemical composition of the sample (Yang et al., ðHald Þ
fald ¼ ð8Þ
C
2003; Patrakov et al., 2005).
Most of the parameters evaluated in the classic methods are %Ci ¼ fi ð%CÞ i ¼ a; al;a; f;b . . . ð9Þ
generally extracted from hypothetical structural models and they   
ð%Ci Þ PM
present a simple calculation method that leads to a direct and ra- #Ci ¼ ð10Þ
1200
tional interpretation of the results, which in turn present a signif-
2     3 
icant semi-quantitative content (Clutter et al., 1972; Williams,   0:33Hc þ 0:4 Hb þ Hmet þ 0:5 Ha þ Hf
C 5 H


1958; Brown and Ladner, 1960; Cantor, 1978). Therefore, some ¼4   ð11Þ
H al Hc þ Hb þ Hmet þ Ha þ Hf C
parameters evaluated in previous works were modified and incor-
porated into our calculation model. These parameters were used to  
ð#Cal  #Cf Þ
characterize the different insoluble fractions of tar in n-heptane L¼ ð12Þ
#Ca
obtained during pyrolysis of pine at the different temperatures,
see description in Table 2.
 D. López et al. / Bioresource Technology 101 (2010) 2458–2465 2461

Table 4 temperature range correspond to low molecular weight com-

Ultimate analysis and average molecular weight of the insoluble fractions of tar in n- pounds. The average molecular weights oscillate between 297 g/
heptane (asphaltenes).
mol and 347 g/mol. The four samples present very similar amounts
Temperature %C %H %N %O (H/ (O/ Molecular weight of C, H and O, and the total H/C and O/C ratios reach a constant va-
(°C) C) C) (g/mol) lue of about 1.4 and 0.6, respectively, which indicates that the sam-
250 52.5 6.4 0.2 41.0 1.46 0.59 347 ples present similar chemical composition. This means that in this
300 52.2 6.2 0.2 41.4 1.42 0.60 306 temperature range there are no significant changes in the nature of
350 51.4 6.2 0.1 42.3 1.45 0.62 299
400 53.4 6.5 0.2 40.0 1.46 0.56 297
the tar produced by pyrolysis of Pine wood.
Fig. 2 shows the 1H NMR spectrum of the insoluble tar fraction
in n-heptane obtained at 300 °C. In the same figure, it is possible to
observe the classification of the different types of hydrogen. The
phatic groups are mainly linear aliphatic chains, where the C/ main assigned groups correspond to: aldehyde proton adjacent to
H = 0.33 ratio in c position, the C/H = 0.4 ratio in b position is an an aromatic ring (Hald), hydrogen on aromatic rings (Ha), olefinic
average value between CH2 and CH3 groups. In the remaining posi- hydrogen (Ho), hydrogen on carbon connecting two aromatic units
tions (a and f) a C/H ratio of 0.5 is assumed. Nevertheless, this or fluorene type (Hf), hydrogen in O–CH3 and O–CH2 groups (Hmet),
assumption breaks down when the branching degree of the ali- hydrogen of CH2 groups on a position to aromatic rings (Ha),
phatic chains among samples increases. hydrogen of CH2 and CH3 groups on b position to aromatic rings
(Hb), and hydrogen of terminal methyl groups on c, d or greater
positions to aromatic rings.
3. Results and discussion The limits of integration for each hydrogen type en the spec-
trum were selected using the classification done by Guillen et al.
One of the most important factors to keep in mind in a discus- (1998) which was obtained from a blend of model compounds,
sion about chemical transformations in pyrolysis processes is the the cut points in the spectra could be identified with much more
temperature. Tars are formed during pyrolysis in a series of com- precision and the range of the different hydrogen groups could
plex reactions. The formation of tar is highly dependent on the be determined in this way and the presence of some additional sig-
reaction conditions. The higher the reaction temperature the larger nals were corroborated with the information already published in
the secondary reactions become, particularly in the gas phase, the literature (Hosoya et al., 2008; Sutcu, 2008).
where oxygenated tar compounds are converted to light hydrocar- Fig. 3a and b present the 1H NMR spectra obtained for the tar
bons, aromatics, oxygenates and olefins subsequently forming fractions (asphaltenes and maltenes) at different temperatures. It
higher hydrocarbons and larger PAH in tertiary processes (Chun- can be seen that there are no major differences in the main signals
shan and Kenzi, 2008). In the experiments here described the con- for each fraction, but there is difference in the intensity of each
versions to liquid and gases at 250 °C and 400 °C were 40% and type of proton according to the pyrolysis temperature. Using this
72%, respectively. information, the weight percent distribution of the different hydro-
Table 4 summarizes the elemental analysis and the average gen types observed by 1H NMR was calculated.
molecular weight of the different tar fractions. The average molec- Table 5 shows the weight percent distribution of the different
ular weight obtained by VPO indicates that tars produced in this hydrogen types observed by 1H NMR for the different tar fractions,

Fig. 2. 1H NMR spectrum of the wood tar fraction insoluble in n-heptane obtained at 300 °C.
2462 D. López et al. / Bioresource Technology 101 (2010) 2458–2465

Fig. 3. 1H NMR spectra of the insoluble tar fraction (asphaltenes) (a) and the soluble tar fraction (maltenes) (b) in n-heptane obtained at different temperatures.

calculated based on the total hydrogen content obtained by ele-
mental analysis. In general, both fractions show variability in the
amount of each type of proton. The amount of aldehydic proton
is greater for the fraction of asphaltenes compared with the frac-
tion of maltenes at the same temperature, while the amount of
aromatic and aliphatic protons in b and c positions is significantly
higher in maltenes than in the asphaltenes fractions at the same
temperature. The amount of protons in methoxy and ethoxy
groups is higher in the fraction of asphaltenes than in the maltenes
fraction, the same behavior is observed for hydrogen fractions Hf,
Ho and Ha.
The above observations are in agreement with the literature,
from the point of view of the insolubility of asphaltenes in n-hep-
tane, which suggests that these compounds have greater amount
of polar groups such as aldehydes and heteroatoms and fewer
amount of aliphatic chains which are characteristic of the maltenes
fraction (Demirbas, 2002; Matthew et al., 2003).
3.1. Average structural parameters of asphaltenes fraction
Nuclear magnetic resonance of proton and carbon are tech-
niques that have been useful in determining the structural skeleton
of several fossil fuels (Clutter et al., 1972; Williams, 1958; Brown
and Ladner, 1960; Cantor, 1978; Guillen et al., 1998; Santamaría
et al., 2007). However, neither the NMR spectra, nor other spectro-
scopic analysis data provide enough information to fully define the
components of a mixture. Therefore, due to the complexity of the
mixture and the need to represent the composition of these frac-
 D. López et al. / Bioresource Technology 101 (2010) 2458–2465 2463

Table 5 describes a similar behavior with values from 0.46 to 0.50, being
Weight percent distribution of the different hydrogen types observed by 1H NMR for these values slightly higher than the ones for the aromatic fraction
the asphaltenes (A) and maltenes (M) fractions.
in the same range of temperature.
250 °C 300 °C 350 °C 400 °C For the fraction of aromatic carbons substituted by aromatic
%Hald A 0.9 ± 0.1 1.6 ± 0.6 0.9 ± 0.3 1.4 ± 0.4 hydrogen (faHa) the values range between 0.17 and 0.23, this result
M 0.3 ± 0.1 0.8 ± 0.7 0.6 ± 0.2 0.3 ± 0.1 implies a small amount of aromatic carbon substituted by hydro-
%Ha A 11.3 ± 0.1 15.9 ± 4.4 12.0 ± 0.7 12.8 ± 2.7 gen, in other words a high substitution degree with other type of
M 17.8 ± 1.0 16.8 ± 2.7 14.8 ± 2.0 18.3 ± 2.6
%Ho A 5.3 ± 1.0 8.5 ± 1.0 5.6 ± 1.6 6.8 ± 2.0
substituent’s.
M 4.7 ± 0.8 3.5 ± 2.5 2.5 ± 1.4 4.5 ± 1.3 Another important parameter that is associated with the degree
%Hf A 8.9 ± 1.0 6.2 ± 1.1 8.8 ± 1.7 6.2 ± 0.6 of aliphatic substitution is fa, which presents values from 0.13 to
M 2.2 ± 0.4 0.8 ± 0.5 1.1 ± 0.6 0.4 ± 0.2 0.16 indicating similar degree of substitution. However, the error
%Hmet A 21.4 ± 0.4 17.1 ± 1.9 22.7 ± 0.2 21.4 ± 2.8
involved in this parameter is relatively high (10% < error < 20%);
M 12.6 ± 0.2 11.0 ± 0.7 13.2 ± 1.8 13.8 ± 0.7
%Ha A 18.0 ± 0.4 22.4 ± 2.4 18.9 ± 1.3 21.2 ± 1.4 leading to an underestimation of the number of a carbons (#Ca)
M 14.6 ± 0.5 16.0 ± 1.0 17.5 ± 1.1 17.5 ± 1.1 which also affects the average chain length calculation (L). A good
%Hb A 22.6 ± 1.3 20.3 ± 1.2 22.1 ± 2.0 20.6 ± 4.4 approximation can be made if the aliphatic carbon number (#Cal)
M 29.1 ± 0.8 30.0 ± 2.5 33.4 ± 1.8 28.0 ± 1.1 present in the samples is taken into account, the average chain
%Hc A 11.6 ± 1.1 7.9 ± 2.5 9.0 ± 2.9 9.6 ± 1.6
length (L) can be estimated in a much more precise way using
M 18.7 ± 1.6 21.3 ± 2.4 17.0 ± 2.8 17.1 ± 3.0
Eq. (12) (Table 3).
Another parameter is the fraction of carbon in carbonyl groups
tions in a systematic way, the concept of ‘‘average structure” has
of aldehydes (fald), which is in the range of 0.01–0.02, although this
gained importance. The structural analysis is generally based on
corresponds to the lowest fraction found in these samples, also
information from nuclear magnetic resonance in combination with
indicates the presence of this functional group, which is present
other analytical techniques (Santamaría, 2007).
in the main components of wood (Fassinou et al., 2009).
Using the H NMR, molecular weight and elemental analysis data
The fraction of carbons in methoxy and ethoxy groups (fmet) is
the average structural parameters such as aliphatic chain length,
in the range of 0.10–1.12, which is in agreement with the high
aromaticity, branching degree of the aliphatic chains, etc., were
amount of oxygenated species present in tars from wood (see Table
calculated for each one of the asphaltenes fractions.
4) and the high concentration of protons in this region of the spec-
The results of average structural parameters for the asphaltenes
trum (see Fig. 3), it is also observed that this fraction does not vary
fraction of tars obtained at different temperatures are summarized
in the range of working temperatures.
in Table 6, where several features are observed. The fraction of aro-
Other important parameters are the number of aromatic car-
matic carbon or aromaticity of the samples (fa) evaluated in this
bons (#Ca) and the number of aliphatic carbons (#Cal), their values
study is in the range of 0.39–0.41, indicating that there is no in-
are in the ranges of 5.21–6.04 and 6.34–6.86, respectively, indicat-
crease in the amount of aromatic carbon as the pyrolysis tempera-
ing that the average molecular structure of the asphaltenes frac-
ture goes from 250 °C to 400 °C. The aliphatic component (fal)
tions of tars produced during the pyrolysis of pine is constituted
by one aromatic ring with aliphatic substitutions and several func-
Table 6 tional groups. The length of the aliphatic chain (L) as alkyl substi-
Average structural parameters results of the asphaltenes fraction of tar obtained at
tuent of the aromatic ring is in the range of 2.55–3.34 which
different temperatures.
indicates that this substitution is in agreement with the studied
Parameter 250 °C 300 °C 350 °C 400 °C carbon positions (a, b and c) to the aromatic ring, so the chains
fa 0.41 0.40 0.41 0.39 are not too long.
fal 0.50 0.46 0.50 0.49 The number of olefinic carbons (#Co) present in the samples is
fa 0.13 0.16 0.14 0.15
in the range of 1.02–1.83, indicating one double bond in the aver-
ff 0.06 0.04 0.06 0.05
fb 0.13 0.12 0.13 0.12 age structure of this fraction of tar.
faHa 0.17 0.23 0.17 0.19 The carbon/hydrogen molar ratio in the aliphatic groups ðC=HÞal
fald 0.01 0.02 0.01 0.02 is in the range of 0.61–0.80, indicating that the fraction of aliphatic
fmet 0.12 0.10 0.13 0.12 groups does not vary significantly with temperature and is slightly
fc 0.05 0.03 0.04 0.04
fo 0.08 0.12 0.08 0.10
higher compared to aromatic fraction.
%Ca 21.4 20.9 21.2 21.0 With the information described above, it can be said that the
%Cal 26.4 23.7 25.5 26.0 average structural parameters of the asphaltenes fractions of tars,
%Ca 6.89 8.40 6.98 8.25 produced during the pyrolysis of pine between 250 °C and
%Cf 3.39 2.34 3.26 2.41
400 °C, do not present significant differences, and therefore the
%Cb 6.90 6.08 6.52 6.41
%CaHa 8.66 11.9 8.84 10.0 fractions of tar contain similar structures.
%Cald 0.67 1.23 0.67 1.07 It is important to mention that the average structural parameters
%Cmet 6.56 5.13 6.70 6.67 give information about hypothetical structures that might be pres-
%Cc 2.66 1.77 1.99 2.25 ent in real samples. However, the qualitative and semi-quantitative
%Co 4.05 6.33 4.11 5.30
#Ca 5.45 6.04 5.27 5.21
information that can be extracted from these parameters is impor-
#Cal 6.73 6.86 6.34 6.43 tant for the interpretation of different chemical processes that affect
#Ca 1.76 2.43 1.74 2.04 the components of the wood on the pyrolysis process and the pos-
#Cf 0.86 0.68 0.81 0.60 sible application of these model compounds in processes such as
#Cb 1.76 1.76 1.63 1.59
reforming and gasification (Swierczynski et al., 2008).
#CaHa 2.21 3.45 2.20 2.48
#Cald 0.17 0.36 0.17 0.26
#Cmet 1.67 1.48 1.67 1.65 3.2. Elucidation of possible average structures of asphaltenes fraction
#Cc 0.68 0.51 0.49 0.56 from tar
#Co 1.03 1.83 1.02 1.31
L 3.34 2.55 3.18 2.86
With the average structural parameters determined in this
ðC=HÞal 0.61 0.80 0.61 0.62
study, it is possible to propose some average structures units as
2464 D. López et al. / Bioresource Technology 101 (2010) 2458–2465

Table 7
Proposed structural units of the asphaltenes fractions and their corresponding structural parameters.

Structure Name PM (g/mol) (fa) (fal)

2,3,5-Trimethoxy-6-[(1E)-prop-1-en-1-yl]-4-propylbenzaldehyde 278 0.36 0.50

4-Formyl-2,6-dimethoxy-3-[(1E)-prop-1-en-1-yl]-5-propylbenzoic acid 292 0.38 0.37

4-Hydroxy-3,5-dimethoxy-2-[(1E)-prop-1-en-1-yl]-6-propylbenzaldehyde 264 0.33 0.40

5-Ethoxy-3-methoxy-2-[(1E)-prop-1-en-1-yl]-4-propylbenzaldehyde 262 0.41 0.41

components of the low temperature tar from pine wood. Based on oxygenates compounds that are in agreement with the proposed
the structural parameters obtained in this research as well as in the structures.
data published in the literature (Evans and Milne, 1987a,b) for
compounds formed during the pyrolysis of wood, four possible
4. Conclusions
average structural units are proposed as shown in Table 7.
These proposed structural units are possible components pres-
The major fraction of tar obtained during pyrolysis of pine at
ent in the insoluble fraction of tar in n-heptane, which fulfill most
different temperatures was the insoluble fraction in n-heptane
of the found average structural parameters. However, it is impor-
which corresponds to asphaltenes (complex hydrocarbons mixture
tant to notice that a large number of similar isomers can be ad-
composed by aromatic rings with alkyl side chains and hetero-
justed to these parameters.
atomic side-chain functional groups).
In the literature (Evans and Milne, 1987a) there are reports
With the structural parameters determined for the asphaltenes
about some possible structures that may be present in tars, which
some average structures were proposed which correspond to one
have been determined by mass spectrometry or chromatographic
aromatic ring which is substituted by aliphatic chains, olefinic
analysis. Concerning the aromatic carbons, these structures are
groups and the presence of oxygenated groups, which is in agree-
similar to those determined in this study. However, with the pro-
ment with those reported in the literature for this type of biomass.
cedure here used we can have a better description of the degree
Using the methodology proposed in this study, it is possible to
of substitution of the aromatic ring.
elucidate an average structure of tars which is required for differ-
The presence of functional groups such as carboxylic acids,
ent applications, either in the energetic field or as an additive in the
ethers or aldehydes in the structure, is attributed to the pyrolysis
production of other products.
of complex structures in the components of wood which decom-
pose in the range of temperature from 200 °C to 400 °C. For exam-
ple, the decomposition of lignin produces phenolic compounds of Acknowledgements
low molecular weight such as syringol (2,6-dimethoxy-phenol),
eugenol (2-methoxy-4-(2-propenyl) phenol) and 1,4-methoxy- We thank to the University of Antioquia for the financing of the
phenol, and other substituted aromatic compounds such as 2- Sostenibilidad program 2009–2010. N.A thanks to the Young Re-
methoxy-4-propyl-phenol, vaniline, 4-methyl-2-methoxy-phenol, search Program of the University of Antioquia for the financing
and highly oxygenated compounds. support.
Among the compounds derived from the thermal degradation of
polysaccharides (cellulose and hemicellulose), the most important
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